Catalytic process for preparing triazines and nitrile polymers

ABSTRACT

THIS INVENTION (A) RELATES TO A PROCESS FOR PREPARING TRIAZINES, NITRILE POLYMERS, AND CROSS-LINKED POLYMERS OR COPOLYMERS BY (1) CONDENSING A NITRILE IN THE PRESENCE OF OR (2) CONTACTING A POLYMER OR COPOLYMER WITH A METAL OXIDE CATALYST SELECTED FROM THE PERIODIC TABLE GROUPS I-B, II-A, II-B, III, IV, V, VII-B, AND VIII, PREFERABLY GROUPS I-B, II-A, II-B, III, IV-A, AND V-A SUCH AS SILVER OXIDE, MERCURIC OXIDE, CUPRIC OXIDE, CADMIUM OXIDE, THE OXIDES OF LEAD, ANTIMONY OXIDE, BARIUM OXIDE, THALLIUM OXIDE, AND ZINC OXIDE, THE NITRILE TYPICALLY BEING PERFLUOROBUTYRONITRILE, DIFLUOROACETONITRILE, DIFLUOROCHLOROACETONITRILE, PERFLUOROGLUTARONITRILE, PERFLUOROSUCCINONITRILE, BENZONITRILE, TRIFLUOROACETONITRILE, PENTAFLUOROPROPIONITRILE, PERFLUOROMALONONITRILE, BROMOTETRAFLUOROPROPIONITRILE, TRICHLOROACETONITRILE, BROMOOCTAFLUOROVALERONITRILE, PERFLUOROOCTANONITRILE, BROMOHEXAFLUROBUTYRONITRILE, AND THE LIKE; AND (B) RELATES TO THE NITRILE POLYMERS AND CROSS-LINKED POLYMERS OR COPOLYMERS PRODUCED BY THE ABOVE PROCESS AND/OR SUCH COMPOUNDS CONTAINING THE ABOVE-IDENTIFIED CATALYSTS.

United States Patent O 3,597,404 CATALYTIC PROCESS FOR PREPARING TRI-AZINES AND NITRILE POLYMERS William E. Emerson and Edwin Dort'man, GrandIsland, N.Y., assignors to Hooker Chemical Corporation, Niagara Falls,N.Y.

N Drawing. Continuation-impart of application Ser. No. 570,183, Aug. 4,1966, which is a continuation-in-part of application Ser. No. 441,331,Mar. 19, 1965, both now abandoned. This application May 1, 1967, Ser.No.

Int. Cl. C081? 3/14 US. Cl. 26088.7 7 Claims ABSTRACT OF THE DISCLOSUREThis invention (A) relates to a process for preparing triazines, nitrilepolymers, and cross-linked polymers or copolymers by (1) condensing anitrile in the presence of or (2) contacting a polymer or copolymer witha metal oxide catalyst selected from the Periodic Table Groups I-B,II-A, II-B, III, IV, V, VII-B, and VIII, preferably Groups I-B, II-A,II-B, III, IV-A, and V-A such as silver oxide, mercuric oxide, cupricoxide, cadmium oxide, the oxides of lead, antimony oxide, barium oxide,thallium oxide, and Zinc oxide, the nitrile typically beingperfluorobutyronitrile, difluoroacetonitrile,difluorochloroacetonitrile, perfluoroglutaronitrile,perfluorosuccinonitrile, benzonitrile, trifiuoroacetonitrile,pentafluoropropionitrile, perfluoromalononitrile,bromotetrafluoropropionitrile, trichloroacetonitrile,bromooctafluorovaleronitrile, perfiuorooctanonitrile,bromohexafluorobutyronitrile, and the like; and (B) relates to thenitrile polymers and cross-linked polymers or copolymers produced by theabove process and/ or such compounds containing the above-identifiedcatalysts.

This is a continuation-in-part of Ser. No. 570,183, filed Aug. 4, 1966,now abandoned which is a continuation-in-part of Ser. No. 441,331, filedMar. 19, 1965, now abandoned.

BACKGROUND OF THE INVENTION Prior to the filing of this application,triazines have been produced from nitriles by the employment of acatalytic amount of a catalytic composition. For example, US. Pat.3,095,414 employs a combination of ingredients which jointly have acatalytic effect sutficiently to convert a nitrile into a triazine.Another example is copending application Ser. No. 594,997 filed November17, 1966 which is directed to the novel process of producing triazine bycondensing a nitrile in the presence of a metal such as copper, iron,indium, bismuth, lead, tin, thallium, zinc, barium and cadmium.

Literature has been published which discloses thatperfluoroalkylenetriazine polymers which do not contain nitrile groupsmay be cross-linked by reaction with tetraphenyltin. However, it hasbeen discovered that the degree of cross-linking is merely a minoramount and is normally insufficient for practical use in utilitiesrequiring a substantial degree of cross-linking.

An object of this invention is a novel process for producing (1)triazines and/or (2) nitrile polymers, by the employment of a criticalcatalyst.

Another object of this invention is a novel composition of polymers orcopolymers including a critical catalyst.

Another object is a process of cross-linking particular polymers orcopolymers by the employment of a critical catalyst.

Another object is a polymer or copolymer composition containing acritical catalyst which makes possible the process of this invention.

Another object is a cross-linked polymer or copolymer compositioncontaining the catalyst of this invention.

Another object is a new use of the polymer or copolymer composition ofthis invention.

Other objects of this invention become apparent from the above andfollowing disclosure.

THE DESCRIPTION The present invention relates to a novel process forpreparing triazines, nitrile polymers, and cross-linked polymers orcopolymers by 1) condensing in the intimate presence of or (2)contacting with a metal oxide, (a) a nitrile or (b) a polymer orcopolymer which contains an average of at least more than one nitrilegroup per molecule of said polymer or copolymer, and relates to noveltriazines, nitrile polymers, polymer or copolymer compositions andcross-linked forms of the polymer or copolymer compositions. Thisinvention also includes polymers or copolymers produced by processesother than the processes disclosed herein, provided that the finalcomposition has a catalyst of this invention dispersed therein.

The preceding paragraph refers to the necessity of an average of atleast more than one nitrile group per molecule. Thereby, this inventionrequires 1) that at least one polymer or copolymer molecule contain twonitrile groups and (2) that each molecule contain at least one nitrilegroup. Any polymer or copolymer molecule that does not contain at leastone nitrile group is not a part of those molecules upon which theaverage of greater than one per molecule is based; a polymer orcopolymer not containing a nitrile group would constitute merely afiller material. In a like manner, the language at least greater than anaverage of one eyanofluoroalkyl group per molecule has the same meaning.Also it should be noted that the degree of cross-linking increases witha corresponding increase in the number of nitrile groups per molecule.The optimum number of nitrile groups per molecule will therefore dependupon the properties desired for a particular use. Also, the optimumnumber of nitrile group on the molecule depends upon the molecularweight of the polymer or copolymer employed. It should be noted that itis within the scope of this invention to employ polymers or copolymerssuch as triazine polymers which may be degraded by some means such as bymilling, for example, to produce fragments, some of which contain thenitrile groups.

The polymers or copolymers of this invention, and cross-linked formsthereof, i.e., those which contain the catalyst of this invention, areeach characterized by novel properties and uses which are distinct fromthe properties of conventional cross-linked polymers produced by otherprocesses which do not contain the catalyst of this invention. However,in addition to new uses based on the novel properties, the compositionsof this invention may be employed for conventional uses of conventionaltriazines and cross-linked polymers.

Preferred polymers or copolymers include at least greater than anaverage of one cyanoperfluoroalkyl group per molecule in which thealkylene is methylene, ethylene, propylene, butylene, pentylene,hexylene, heptylene, octylene, nonylene, decylene, and the like.However, higher alkylene groups may be employed.

The nitrile is of the formula:

PQCN

wherein Q is selected from the group consisting of F -''CXYmZuOGLnW L()b-Jd and wherein:

(a) X and G are selected from the group consisting of chlorine,fluorine, bromine, and iodine;

(b) Y and L are selected from the group consisting of hydrogen,fluorine, chlorine, bromine, iodine, alkyl of 1 to 20 carbon atoms,haloalkyl of 1 to 25 carbon atoms, aryl of 6 to 20 carbon atoms,perhaloalkyl, perhaloalkenyl of 1 to 25 carbon aoms, nitrile, andcyanoperhaloalkyl;

(c) m and n are integers, the sum of which must be at least one;

(d) Z and W are selected from the group consisting of --CXY--, CGL--,perhalo lower alkylidene of 1 to 12 carbon atoms, perhalo lower alkyleneof 1 to 12 carbon atoms, carbonyl, oxy, sulfinyl, thio, thiocarbonyl,diazo, tetrafiuorothio, sulfonyl, alkylene radicals of the formula:

wherein a ranges from to 1, u ranges from 1 to 10, and m and n are ashereinbefore defined, and N-substituted azaalkylene radicals of theformula:

wherein R; is selected from the group consisting of fluorine andperfluoroalkyl groups of 1 to 12 carbon atoms, and a, u (eachoccurrence), m, and n are as herein defined.

(e) a (each occurrence), [1, and d range from 0 to 1;

(f) P is selected from the group consisting of hydrogen,

fluorine, chlorine, bromine, iodine, and nitrile; and

(g) E, I, J, and K are selected from the group consisting of hydrogen,fluorine, chlorine, bromine, iodine, alkyl of about 1 to 10 carbonatoms, aryl of 6 to 20 carbon atoms, arylcarbonyl of 6 to 20 carbonatoms and nitrile.

The novel products formed by said process are of the compositionincluding the critical catalyst of this invention dispersedsubstantially uniformly throughout a compound of the formula (PQCN)wherein y is from 2 to 20. If a mononitrile is the starting material,said nitrile will generally all be converted to a triazine when used inthe process of this invention. When either the barium 0X- ide orthallium oxide catalyst is used, however, a small amount of themononitrile will not be converted to the triazine; nontriazinecondensation products are formed.

When a dior polynitrile is the starting material, said nitrile, whenused in the process of this invention, is converted into nitrilecondensation products, such as dimers, trimers, tetramers, and similarlow, medium, and high molecular weight insoluble polymers. If aperfluoroalkane nitrile of 5 to 25 carbons is used, novel triazines areobtained. Similarly, if perfluoroglutaronitrile,perfluorosuccinonitrile, perfiuoroadiponitrile, orperfluoromalononitrile is used as a polynitrile, novel non-triazinecondensation products are obtained.

A mixture of nitriles may be used to obtain a mixture of triazines. Forexample, if a mixture of trifluoroacetonitrile andperfluorooctanonitrile is condensed, three different novel triazineproducts are obtained as shown below, the triazine without theperfiuoroheptyl group being old in the art.

Metal oxide OFaCN C1Fi5CN Catalyst NN NN CFa C1Fis P (CF CN wherein P isas liereinbefore defined and wherein when P is fluorine or chlorine nranges from 1 to 12, and wherein when P is bromine or iodine, n rangesfrom 2 to 12; those of the formula:

wherein D is selected from the group consisting of oxygen,tetrafluoro-sulfur groups, and wherein n and in range from 1 to 12, andP is as hereinbefore defined; and those of the formula wherein p, n, andm range from 1 to 12, and wherein P is as hereinbefore defined. Some ofthe especially preferred nitriles represented by said formulae includeperfiuorobutyronitrile, difluoroacetonitrile,difluorochloroacetonitrile, perfluoroglutaronitrile,perfluorosuccinonitrile, trifluoroacetonitrile,pentafluoropropionitrile, perfluoromalonitrile,bromotetrafluoropropionitrile, bromooctafiuorovaleronitrile, nonoafluoro3 thiabutyronitrile, perfluoroethyladiponitrile, perfiuorosuberonitrile,perfluorosebaconitrile, perfluorovaleronitrile, 4bromohexafluorobutyronitrile, perfluoroadiponitrile,perfluorotetradecane dinitrile, perfluoromethoxypropionitrile, andperfluoroethoxypropionitrile, trichloroacetonitrile, andperfluorooctanonitrile.

Other nitriles which are operative in the process of this inventioninclude, e.g., perfluorocapronitrile; 3,4dibromopentafiuorobutyronitrile; trifiuoromethylbenzonitrile;chlorobenzonitrile; dichlorobenzonitrile; polychlorobenzonitriles;perfiuorododecanenitrile; perfluorotetr-adecane nitrile;perfluorostearonitrile; benzonitrile; 2nitro-4-trifluoromethylbenzonitrile; perfluorooleonitrile; m(trifiuoromethylbenozyl)benzonitrile; 2 phenyl 2,4,4,4-tetrafiuoroacetoacetonitrile; perfiuorobenzonitrile; nitriles Of thefOImula.

(I|h R f0 m wherein R, is lower per' fiuoroalkyl and R is selected fromthe group consisting of fluorine, and perfluoroalkyl of from 1 to 12carbon atoms, such as CFaOCFzCFzCN, CFaCFzOFCN and the like; nitriles ofthe formula T(R ")(CF ),,CN

wherein T is selected from the group consisting of hydrogen and halogen,'Rf is perfluoroalkylene of 1 to 12 carbon atoms, and n is from 1 to 10,such as perfluoroisobutyloxypropionitrile,perfluorohexyloxypropionitrile, perfiuorooctyloxypropionitrile, and thelike; and mixtures of the aforementioned nitriles.

The catalysts employed in the process of this invention are oxides ofthe metals of Groups I-B, II-A, II-B, III, IV, V, VII-B, and VIII of thePeriodic Table, preferably those of Groups I-B, II-A, II-B, III, IVA,and V-A. Among the specially preferred metal oxide catalysts are silveroxide, mercuric oxide, cupric oxide, cadmium oxide, the oxides of lead,red lead oxide 1e 0, antimony oxide, barium oxide, cuprous oxide,thallium oxide, and zinc oxide. The catalysts of this invention may beused in any catalytic amount from 0.01 to percent by weight of thenitrile to be condensed. Preferably, the catalyst will be employed in anamount between 0.05 to 6 percent by weight of the nitrile to becondensed. The above catalysts of this invention may be used alone or incombination, for the invention disclosed herein.

The nitrile condensation reaction may be run in any solvent which doesnot react with the nitrile, the catalyst, or the reaction products ofthe nitrile and catalyst. Suitable solvents include, e.g., n-butylacetate, carbon tetrachloride, ortho-chlorotoluene, chlorobenzene,nitrobenzene, cyclohexanone, ortho-dichlorobenzene, diethylcarbitol,dimethylsulfoxide, dioxane, ethyl acetate, and the like. This list ismerely illustrative, and does not purport to describe the vast number ofsolvents which can be used in the process of this invention.

The novel process of this invention for producing the triazines, nitrilepolymers and cross-linked polymers or copolymers is operable at atemperature of from 0 to 400 degrees centigrade, though it is preferredto work in the 25 to 250 degrees centigrade range, and an even morepreferred temperature range is that of from about 25 to 190 degreescentigrade. The process of this invention is operable at atmospheric orautogenous pressures.

The reaction time is dependent on the catalyst employed, the amount ofcatalyst employed, the temperature at which the reaction is carried out,and the degree of convefsion desired. Reaction times of from about fourhours to about seven days are satisfactory.

The triazines, nitrile polymers, and cross-linked polymers or copolymersproduced by the above process of this invention are useful inapplications (uses) requiring high temperature stability. The noveltriazines of this invention are useful both as high temperaturelubricants and solvents, and the nitrile polymers produced by the aboveprocess when a dinitrile is condensed, and which contain the criticalcatalyst of this invention, are useful in the preparing of cross-linkedhighly heat-resistant molded articles.

A novel mixture of this invention useful in preparing a cross-linkedpolymer or copolymer composition, and useful for employment as a hightemperature sealant includes a polymer or copolymer in combination withthe metal oxide catalyst of this invention. In a second novel mixture,the above polymer or copolymer is a cross-linked structure.

The novel process of this invention includes the steps of curing, i.e.cross-linking a polymer or copolymer described above containing asufiicient number of nitrile groups, the curing being (1) at asufficiently elevated temperature and for a period sutficiently long and(2) in the intimate presence of the above described critical catalyst ofthis invention, to cross-link (vulcanize) to form a cross-linked polymeror a cross-linked copolymer.

The cross-linking process of this invention may (for example) employ anypolymeric composition having at least greater than an average of onecyanohaloalkyl group per molecule in the novel presence of a catalyticamount of the catalyst of this invention to crosslink to form across-linked polymer or copolymer. The crosslinked former cyanogroup-containing polymers and copolymers of the novel curing processexhibit novel properties. The particular properties depend, for example,upon which particular catalystof this invention is employed, the filleremployed, the polymer or copolymer molecular weight, the number ofnitrile groups on the molecule and the like.

The degree of cross-linking for polymers and copolymers of thisinvention has been found to typically depend on the number ofcyanohaloalkyl groups along the polymer chain, the amount of catalystused, and on the time and the temperature range which is used in thecuring process of the polymer. The polymers which have been cross-linkedby this method have been perfluoroalkylenetriazine polymers of a widerange of molecular weight. The particular curing temperature necessarytypically depends upon which catalyst is employed, the amount ofcatalyst employed, the particular polymer or copolymer, and the durationof curing. Normally the curing temperature is at least about 25 C., upto about 200 C., for example, preferably up to about 150 C.

Lower molecular weight perfluoroalkylenetriazine polymers which havenitrile groups only at the polymer chain ends have been curedcatalytically. Perfluoroalkylenetriazine polymers which havecyanoperfiuoroalkyl groups at the 6 position of the triazine ring havealso been successfully cured. The percentage of cyanoperfluoroalkylgroups at the 6 position of the triazine ring on these polymer moleculesmay vary from less than 1 percent up to percent. A preferred percentageis from about 3 percent to 20 percent of nitrile-containing groups inthe 6 position of the triazine ring. Perfluoroalkylenetriazine polymershave been described in. our copending application U.S. Ser. No. 533,430,which disclosure is hereby incorporated by reference.

Other fluorine-containing polymers such as thetetrafluoroethylene-trifluoronitrosomethane copolymers might also becured by these catalytic curing processes. Perfluoroalkylene etherpolymers, perfiuoropropylenevinylidene fluoride copolymers, fiuoroalkylsilicone polymers and the like also may be cured by the catalyst.

The following examples are not intended to limit the invention disclosedherein except to the extent that limitations are specifically stated orto the extent to which limitations appear in the appended claims. Theinvention is illustrated by the following non-limiting examples in whichtemperatures are expressed in degrees centigrade, and parts are byweight, unless otherwise indicated.

EXAMPLE 1 To a glass autoclave containing one part of silver.

oxide were charged 130 parts of perfluorobutyronitrile. The vessel wassealed under nitrogen and heated at 70 degrees centigrade, the pressurebeing approximately 115 pounds per square inch gauge. After 24 hours,the pressure had dropped to approximately pounds per square inch gauge.Thereupon, the temperature was raised to 80 degrees centigrade andmaintained there for the next six days while the pressure graduallydropped to approximately 20 pounds per square inch gauge. The autoclavewas then cooled, the pressure was reduced to zero pounds per square inchgauge, and thereafter the autoclave was opened and the contents werefiltered. The product was distilled at 42 to 45 degrees centigrade and apressure of one millimeter of mercury to obtain 128 parts product whichwas identified by its infrared absorption spectrum as tris(perfluoropropyl) triazine. The residue contained 0.2 part of silveroxide.

EXAMPLE 2.

One part of silver oxide and 100 parts of perfluorooctanonitrile wereheated at 110 degrees centigrade for a period of four days.Tris(perfluoroheptyl)triazine with a boiling point of 130 degrees at0.025 millimeter of mercury, was recovered by distillation in 93 percentyield. It was characterized by infrared absorption at 1550- reciprocalcentimeters for the triazine ring and 1200-1250 reciprocal centimetersfor the C-F absorptions.

EXAMPLE 3 Example 2 was repeated except that five parts of silver oxidewere used. The reaction was completed in eight hours and the sameproduct was recovered with substantially the same yield.

EXAMPLE 4 Using the procedure of Example 1, ten parts ofperfluoroglutaronitrile were condensed in a glass autoclave containing0.1 part of silver oxide catalyst. The resulting yellow-white compoundhad typical C=NC:N infrared absorption bands at 1624 and 1690 reciprocalcentimeters. The melting point of the sublimate began were charged partsof benzonitrile. The temperature was maintained at approximately 115degrees centigrade for 132 hours. The reaction product was 2,4,6-tris-(phenyl)-1,3,5-triazine.

In a like manner perfluorobenzonitrile was condensed by the procedure ofExample 7.

EXAMPLE 8 Example 2 was repeated except that the catalyst was cadmiumoxide. The reaction was allowed to proceed for 22 hrs. at 190 C. Thereaction product was identified by an infrared absorption spectrum to betris(perfiuoroheptyl)triazine, in 100% yield and 87% conversion.

EXAMPLE 9 Example 2 Was repeated except that the catalyst was red leadoxide (Pb O Again, the reaction was allowed to continue for 20'hrs. at190 C. after which the reaction product was identified as being the sameas the reaction product of Examples 2 and 8. The yield and conversionwere about 100%.

The product of Examples 4, 5 and 6 is useful in preparing molded objectshaving high thermal stability which are useful as fittings, couplingsand gaskets by the application of heat. The products of Examples 1through 3 and 7 through 9 are useful as high temperature oils andsolvents.

EXAMPLES 10-3 0 In the following examples, unless otherwise noted underthe Comments section, 3.56 parts of perfluorooctanonitrile were reactedwith the specified catalyst for 20 hours at a temperature of 190 degreecentigrade. The yield of triazine was calculated as from the percent ofnitrile reacted.

Percent 3 Parts of Nltrlle Yield of Example Catalyst catalyst reactedtriazine Comments 0. 089 Trace 100 101 degrees, 69 hours. 0. 210 0. 5100 0. 050 Trace 100 0. 104 100 100 110 degrees. 0. 104 3 100 25degrees, 30 days. 0. 075 0. 3 100 0.072 0.8 100 0.072 Trace 100 110degrees. 0.195 0. 2 100 0.201 70 100 0.215 5 100 0.032 41 100 0. 138 10085 Rest unknown. 0. 131 0. 2 100 0.146 8 100 Small amount unklnown. 0.072 0. 2 70 Rest unknown, 1k0 degrees for 260 hours. 0.206 42 100 Smallamount un nown. 0. 082 0. 2 100 0. 102 Trace 100 Do. 0. 073 2. 3 100 0.069 0. 2 100 Do.

at 125 degrees Centigrade. The recrystallized compound melted at 159degrees. The intrinsic viscosity of the crude product in1,2-dimethoxyethane Was 0.03 deciliters per gram.

EXAMPLE 5 Example 4 Was repeated except that the catalyst was mercuricoxide. Substantially the same physical data were obtained for theresulting product.

EXAMPLE 6 Example 4 was repeated except that the catalyst was cupricoxide. Again, substantially the same physical data were obtained for theresulting product.

EXAMPLE 7 To an autoclave containing 5.6 parts of silver oxide EXAMPLE31 (EXPERIMENTS l-2) 150 centigrade. Postcuring often increases thetensile strength of the vulcanized polymer. For barium oxide and partsof CCI CN produced 90% yield and conversion, respectively, oftris(trichloromethyl)triazine.

zinc oxide, Table II discloses the process conditions and evidence of across-linked product.

TABLE II Temp. Time Experiment No. Catalyst 0.) (ins) Solubility Bariumoxide. 150 97 Insoluble. Zine oxide 150 97 Do.

EXAMPLE 32 A poly(perfluorooctamethyleneperfluoropropyltriazine)containing cyanoperfluoropropyl groups was prepared by addition of 0.72part of 4-cyanoperfiuorbutyryl chloride to parts ofpoly(perfiuorooctamethylenetrizapentadiene), in 37 parts ofdimethoxyethane, with the subsequent addition of 77 parts ofperfluorobutyric anhydride. The product was recovered after removal ofsolvent and volatile by products by distillation and by drying at 150EXAMPLE 3 3 The general procedure of Example 32 was followed tocrosslink (vulcanize) w-cyanohexafluoropropyl-pendant triazine polymerin five consecutive experiments (1-5) employing silver oxide (Ag O) withtriazine polymers having varying amounts of cyano groups therein.Polymers a through e were produced by approximately having more cyanoreactant introduced for b than for a, more for c than for b, more for dthan for c and more for e than for d; however, due to less thancompletely reliable analytical methods, the relative amount of cyanoreactant introduced is not necessarily conclusive evidence that thetriazine polymer contains that relative amount of cyano groups. Theproperties of the resulting cross-linked products are disclosed in TableIII.

EXAMPLE 34 In an additional series of experiments, following a procedureidentical to Examples 10-30, (A) in two separate experiments employingBaO and ZnO at 5 mole percent based on nitrile, respectively, 3.8 partsof Br(CF CN produced 100% yield and conversion, respectively, of a novelcompound, tris(3-bromohexafluoropropyl)triazine, and (B) in two otherseparate experiments employing the above catalysts, respectively, 2.88

Various changes and modifications may be made in the method of thisinvention, certain preferred forms of which have been described andequivalences may be substituted without departing from the spirit andscope of this invention.

What is claimed is:

1. A process for preparing a cross-linked polymer or copolymercomposition which comprises reacting at least one perfluoroalkylenetriazine polymer or copolymer which contains at least one polymer orcopolymer molecule containing two nitrile groups and wherein eachmolecule contains at least one nitrile group, in the presence of acatalytic amount of a metal oxide, at a reaction temperature from zeroto 400 degrees centigrade.

2. The process of claim 1 wherein the catalyst is selected from thegroup consisting of the oxides of Groups I-B; IIA, II-B, III, IV, V,VIIB and VIII of the Periodic Table and mixtures thereof, wherein thereaction temperature is from about 25 to about degrees centigrade andwherein each nitrile group is part of a cyanohaloalkyl group.

3. The process of claim 2 wherein the catalyst is selected from thegroup consisting of silver oxide, mercuric oxide, cupric oxide, cadmiumoxide, plumbous oxide, plumbic oxide, red lead oxide, antimony oxide,barium oxide, thallium oxide, Zinc oxide, and mixtures thereof.

4. The process according to claim 3 wherein the alkylene groups of thecyanohaloalkyl groups are each selected from the group consisting ofmethylene, ethylene, propylene, butylene, pentylene, hexylene,heptylene, octylene, nonylene and decylene.

5. The process according to claim 4 wherein the catalyst is bariumoxide.

6. The process according to claim 4 wherein the catalyst in zinc oxide.

7. The process according to claim 4 wherein the catalyst is silveroxide.

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